Primary alkyl phenol sulphonates



Patented June 25, 1940 UNITED STATES "PATENT orrlcr.

PRDIARY PHENOI SULPHONATES Lawrence H. Flett, Hamburg, N. Y., assignorto National Aniline & Chemical Company, Inc., New York, N. Y., acorporation of New York No Drawing.

Application September 25, 1935,

Serial No. 42,157 1 Y 19 Claims. ('01. 260-512) I This invention relatesto the production of chemical compounds useful as. detergents, wettingagents, emulsifying agents, foaming agents and the like. It relates moreparticularly to a 5. new class of compounds which are derivatives 0MB-CHrgroup and R represents an open-chain hydrocarbon radical(straight-chain or branchedchain, saturated or unsaturated) containing11 or more (preferably 11 to 22, and especially 13 to 18) carbon atoms,and M represents hydrogen or a metal or" an ammonium or organic ammoniumradical. For convenience they will be hereinafter referred to as primaryalkyl phenol sulphonates, which term generically includes the phenol andcresol derivatives, in-the.

water or in acid treating baths or in salt baths.-

They have the further advantage of being in general better wettingagents and more soluble than the usual soaps, and of leaving the washedgoods, with a soft feel. Inasmuch as water solutions of them in the formof their alkali metal salts are neutral in reaction, the latter may besafely used for the washing of delicate silks and 50 other flne fabricsas well as for personal toilet purposes. The said alkyl phenolsulphonates are also valuable wetting agents useful in the textile andrelated fields and as insecticidal, fungicidal, emulsifyin dispersing,and/or tanning agents. 7

are long chain alkyl derivatives of phenol and v in which A representshydrogen or a methyl The compounds ofthe present invention can beprepared, in accordance with one method of procedure, by sulphonatingthe corresponding nuclear alkyl derivative of phenol (hydroxybenzene) orof a cresol (1.2-, 1.3- or 1.4-methyl-hydroxybenzene) having the generalformula in which A represents hydrogen or a methyl group and Rrepresentsan open-chain hydrocarbon radical (straight-chain orbranchedchain,'saturated or unsaturated) containing 11 or more(preferably 11 to 22, and especially 13 to 18) carbon atoms. Forconvenience, such compounds are herein referred to as monoalkyl" phenolcompounds, although they may contain a methyl group in addition when thephenol compound employed is a cresol. The said alkyl phenols and cresolcan be prepared in the known manner, as for example, by condensingbenzene or toluene with a fatty acid or acid'chloride containing thesame number'of carbon atoms as the desired alkyl group,#reducing theresulting "alkyl keto benzene or toluene, for example, by

the Clemmensen method (cf. 8th ,Intemational Congress of AppliedChemistry, 6, 6 8-76 (1912) and Ber. 46, 183"! (1913)); sulphonating theresulting alkyl benzene or toluene, and fusing the resulting sulphonicacid with caustic alkali to form the corresponding alkyl phenol orcresol (cf.- Berichte der Deutschen Chemischen Gesellschaft 19 (1886)2984); or by condensing a fatty acid or fatty acid chloride with phenolor a cresol to produce the corresponding alkyl keto phenol or cresol andreducing the resulting product to the alkyl phenol or cresol. Preferredalkyl phenol products for use in the preparation of alkyl phenolsulphonates in accordance with the present invention comprise the mixedalkyl phenol or cresol products which result from the employment in theabove processes of a mixture.

of fatty acids obtained from naturally occurring vegetable and animaloils and waxes (such as the mixture of fatty acids obtainable fromcocoanut oil, palm kernel oil, spermaceti, and the like).

, drate, oleum), chlorsulphonic acid, etc.

is preferably employed for sulphonation, especially when the product isto be used as a detergent, in view of the resulting superior detergentproperties. Distillation is preferably carried out at a pressure notexceeding mm. to avoid decomposition.

The invention is of particular advantage in that it permits theproduction of products usein] as detergent, wetting, emulsifying,foaming agents, and the like from readily available higher fatty acidswhich in turn can be readily obtained from naturally occurring andrelatively cheap fatty acid esters, for example, oils, fatsand waxes,such as cocoanut oil, stearin, palm kernel oil, olive oil, and the like.The invention is not limited, however, to the employment of higher fattyacids obtained from naturally occurring oils, fats and waxes, butincludes other aliphatic carboxylic acids. 1

As sulphonating agents there may be employed sulphuric acids of variousstrengths (e. g.,

66 B. sulphuric acid, sulphuric acid monohy- The sulphonation may becarried out with the aid of heating or cooling, as required, dependingupon the ease of sulphonation of the alkyl phenol or cresol and thesulphonating P wer of the sulphonating agents. The sulphonation of thealkyl phenol or cresol may be carried out to an extent such that mainlyone, or more or less than one, sulphonic acid group is present in thefinal product (based on the alkyl phenol compound), it depending uponthe properties desired of the final product, as will appear more fullyhereinafter.

The alkyl phenol sulphonates may be prepared in accordance with thepresent invention in the form of their free sulphonic acids or in theform of salts of metals (as for example, of the alkali metals) or oforganic bases, or of ammonia, etc.

The salts may be obtained in any suitable manner, for example byreacting the sulphonated product, either in the crude form resultingfrom the sulphonation or in a purified form, with a metal oxide orhydroxide, ammonia or an organic base, or a suitable salt of one ofthese, in an amount adapted to form a neutral product. Among the bases,oxides and salts which may be combined with the sulphonated products toproduce salts useful as detergents and otherwise are, for examplesodium, potassium and ammonium hydroxides; sodium, potassium andammonium carbonates and bicarbonates; ammonia; magnesium oxide?ethylamine; pyridine; triethanolamine; propanolamines; butanolamine's;diamino propanol; ethylenediamine; triethylene tetramine, etc.

The invention will be illustrated by the following specific examples. Itwill be realized by those skilled in the art that the invention is notlimited thereto, however, except as indicated in the appended patentclaims. The parts are by weight and temperatures are in degreescentigrade.

Emmple 1.-Acetic anhydride (20 parts) is mixed with 100 parts of paranormal cetyl phenol (resulting from the condensation of 1 mol ofpalmitic acid with 1 mol of phenol in the presence of zinc chloride andreduction of the resulting palmitoyl phenol by the Clemmensen method; orby condensing 1 mol of palmitoyl chloride with 1 mol of benzene in thepresence of aluminum chloride, reducing the corresponding ketone by theClemmensen method, sulphonating and fusing the sulphonic acid withcaustic alkali in the usual manner; or by condensing n-cetyl alphahalidewithl benzene, fractionating the resulting product, sulphonating theprimary cetyl benzene and fusing the sulphonic acid with caustic alkaliin the usual manner). To this agitated mixture, '75 parts of 25% oleumare added at such a rate that the temperature of the mix does not exceed50. The mix is warmed to 85 and held at this temperature until a sampleis completely soluble in neutral, acid and alkaline aqueous solutions,

'and a 0.2 per cent neutral solution does not precipitate any calciumsalts "from a solution of a soluble calcium salt containing theequivalent of 0.224 gram calcium oxide per liter. When the sulphonationis completed, the reaction mass is diluted with water to 450 to 600parts and neutralized with alkali; as for example, caustic soda, potash,soda ash, etc., or their equivalents. The neutral solution is clarified,if desired, by filtration and the solution or filtrate is evaporated todryness.

The sulphonate thus obtained may be represented in the form of the freeacid by the probable formula CmHaa-CsHa-(OH)-SO:H, or more particularlyas .orawrmuoHQon oiH Example. 2.-100 parts of the mixed normal alkylphenols obtained by condensing phenol with the mixture of free acidsproduced by saponifying cocoanut fat, to form the mixed ketone phenols,and reducing the ketone phenols by the well known Clemmensen method tothe normal alkyl phenols, and 20 parts of acetic anhydride are mixed,and to this agitated mixture 80 parts of 26% oleum are added at such arate that the temperature of the mix does not exceed 50". The mix isheated to 80 and held at this temperature until the desired degree ofsulphonation has been attained. The mass is diluted with water,neutralized, filtered and evaporated to dryness.

The sulphonated product thus obtained comprises, chiefly, a mixture ofnormal primary alkyl phenol sulphonates in which the alkyl groupsconsist of straight (normal) saturated aliphatic chains containingmainly from 12 to 18 carbon atoms. In the form of the freeacids thelatter may be represented by the following general probable formula inwhich Rn=a normal alkyl group from CHI-I25 to Cid-I31, inclusive.

It will be realized by those skilled in the art that changes may be madein the products, and in the processes of preparing them, hereinbeforedescribed, without departing from the scope of the invention. I

The sulphonation may be carried out in the presence or absence of aninert organic solvent or diluent and in the presence or absence of asulphonation assistant. As solvents or diluent there may be employed anyinert organic liquid which is not readily sulphonated, such ashalogenated hydrocarbons of the aliphatic and aromatic series, as forexample, carbon tetrachloride, dichlorethane, tetrachlorethane,dichlorbenzene, etc. When an-inert solvent or diluent is used, it may beseparated from the alkaline aqueous solution of the sulphonic acid saltof the alkyl phenol which results upon diluting the sulphonation masswith water and neutralizing or it may be separated in the process ofdrying said salt.

As sulphonation assistants there maybe employed' the lower organic acidsand/or their anhydrides, as for example, acetic acid, acetic anhydride,etc.

The temperature at which the sulphonation is carried out may vary withinwide limits. For example, temperature as low as about 0 and as high asabout 140 C. may be employed. v In general the more vigorous thesulphonating agent the lower is the preferred temperature. Ordinarilythe completion of the sulphonation is carried out at a temperature inthe neighborhood of about 25 to about 80 C. The ratio of sulphonatingagent employed with respect to the alkyl phenol also may be varied.While the preferred amounts are given in the above examples, an amountof sulphuric acid or other sulphonating agent equivalent to from 1 toabout 5 parts by weight of sulphuric acid monohydrate per part by weightof the alkyl phenol may be employed.

The extent to which the sulphonation is carried out may vary with theindividual material being sulphonated and the use to be made of thesulphonated product. In general the extent of the sulphonation of thealkyl phenol treated is such as to form chiefly the monosulphonic acidof the alkyl phenol, and to sulphonate impurities as well, if present.

The reaction mixtures resulting from the sulphonation of the alkylphenol or cresol may also be directly employed for the formation ofmixed products, as for example mixtures of salts of the alkyl phenolsulphonic acid and of other acids present in said reaction mixtures,which mixtures of salts are also useful as such. Thus. the sulphonationreaction mixture resulting from the treatment of the alkyl phenol orcresol with an amount of sulphonating agent in excess of thattheoretically required to effect the desired degree of sulphonationmaybe treated with a suitable inorganic or organic base or basic salt(as for example, one'of those hereinbefore mentioned) and the resultingmixture of the salt of the suiphonated allgvlphenol or 'cresol and thesalt of the other acid (as for example, sodium sulphate) may be jointlyisolated from the reaction mixture and employed as such. when it isdesired to produce a salt of the sulphonated alkyl phenol or cresol in aform substantially free from inorganic salts (for example, inorganicsulphates) the alkyl phenol sulphonic acids may be recovered in the freeform by any well-known method for recovering aromatic sulphonic acids.They may also be obtained from the mixed products produced by suchprocesses as are given in the above specific examples by takingadvantage of the solubility of the alkyl phenol sulphonates in the saltform in alcohol and other organic so1- vents. Thus a mixture of a saltof the alkyl phenol sulphonate and an-inorganic sulphate,-

such as the mixed products resulting from the processes of Examples 1and 2} may be extracted with alcohol; and the resulting extract may beevaporated to leave a residue of the purified salt of the sulphonatedproduct, as illustrated by the following specific example:

Example 3.-,-The neutralized solution of normal cetyl phenol sulphonicacid prepared in Example I (or the equivalent aqueous solution preparedfrom the dry sulphonate) is diluted with an equal volume of denaturedalcohol, thoroughly mixed for several hours, a decolorizing charcoal isadded, and the solution is filtered and evaporated to dryness.Alternatively thedry prodbe extracted with successive portions ofdenatured alcohol, the total amount of'alcohol used for-this extractionbeing preferably approximate- 1y four times the weight of the dryunextracted sulphonate, the combined extracts are mixed witha smallamount of animal charcoal, filtered and evaporated to dryness. Theresidue obtained in either case is n-cetyl phenol sulphonatepracticallyfree from inorganic salts of mineral acids. It is preferableto add a small amount of alkali to the alcoholic extract before drying.If'thecrude product before extraction is dark colored, the purifiedsulphonate is lighterin color. The product dissolves very readily inneutral, acid and. alkaline aqueous solutions.

The alkyl phenol sulphonates may also be prepared by employing benzenesulphonic acid, a toluene sulphonic acid, a phenol sulphonic acid, or acrescl sulphonic acid-instead of the benzene,

uct resulting from the process of Example 1 may toluene, phenol andcresol in the processes hereinbefore described, followed byreduction ofthe alkyl keto compound at any stage in the process. The processeshereinbefore described, in which the unsulphonated alkyl phenol isfirst-prepared and then sulphonated are preferred, however.

The sulphonated products in the form of metallic salts or salts ofinorganic bases are usually,,,. yellowish to white, friable solids; andin the form.

of salts or organic bases vary from viscous oils to semi-solids tosolids. are readily soluble in water and in aqueous (neutral, acid oralkaline) solutionsto form solutions which are faintly colored brown oryellow, which are of a soapy nature and which foam readily. Certain ofthe salts, such as the salts of the aromatic monoamines and thealiphaticand-aromatic polyamines, are oils which generally are insolublein water but soluble in organic solvents (as for example, benzene,gasoline, etc.) and in aqueous solutions of alkalis (presumably byconversion-to the salts of the alkalis).

It is to be understood that the invention includes products containing aplurality of alkyl phenol sulphonic acid nuclei linked together throughthe sulphonic acid groups by a polyvalent metal or organic basicradical, as well as products in which an alkyl phenol sulphonic acid islinked through the sulphonic acid groupto a different acid compound by apolyvalent metal or organic basic radical.

Thus the invention comprehends compounds of the type (X) n'Z(X')1. and(X)n-Z (Y)n, wherein X and X each represent the radical.

wherein X and B. have the meaning defined above,

- and W represents a radical containing an acid In general, the saltsgroup at least one of which is a radical of the type represented by X.

This application is a continuation-in-part of applications Serial Nos.691,081 and 691,082, filed September 26, 1933.

I claim:

1. A sulphonated nuclear monoalkyl derivative of phenol and itsmono-methyl derivatives, useful as a detergent, wetting agent,emulsifying agent and the like, having at least 11 carbon atoms in analkyl radical linked to the phenol nucleus by a methylene group.

2. A sulphonated nuclear monoalkyl derivative of phenol and itsmono-methyl derivatives, useful as a detergent, wetting agent,emulsifying agent and the like, having at least 11 carbon atoms in astraight-chain alkyl radical linked to the phenol nucleus by a methylenegroup.

3. A sulphonated nuclear monoalkyl derivative of phenol and itsmonomethyl derivatives useful as a detergent, wetting agent, emulsifyingagent and the like, having at least 11 carbon atoms in a straight-chainsaturated hydrocarbon radical linked to the phenol nucleus by amethylene group.

4. A sulphonated nuclear monoalkyl derivative of phenol and itsmono-methyl derivatives, useful as a. detergent, wetting agent,emulsifying agent and the like, having 11 to 22 carbon atoms in anopen-chain hydrocarbon radical linked to the phenol nucleus by-amethylene group.

5. A sulphonated nuclear monoalkyl derivative of phenol and itsmono-methyl derivatives, useful as a detergent, wetting agent,emulsifying agent and the like, having 13 to 18 carbon atoms in anopen-chain hydrocarbon radical linked to the phenol nucleus by amethylene group.

6. A sulphonated nuclear monoalkyl derivative of phenol and itsmono-methyl derivatives, useful as a detergent, wetting agent,emulsifying agent and the like, having 11 to 22 carbon atoms in astraight-chain hydrocarbon radical linked to the phenol nucleus by amethylene group.

7. A sulphonated nuclear monoalkyl derivative of phenol and itsmono-methyl derivatives, useful as a detergent, wetting agent,emulsifying agent and the like, having 15 carbon atoms in astraight-chain saturated hydrocarbon radical linked to the phenolnucleus by a methylene group.

8. A phenol sulphonate having a single openchain hydrocarbon radicalcontaining at least 11 carbon atoms linked so the phenol nucleus by amethylene group.

9. 'A phenol sulphonate having a single straight-chain saturatedhydrocarbon radical containing at least 11 carbon atoms linked to thephenol nucleus by a methylene group.

10. A phenol sulphonate having a single openchain hydrocarbon radicalcontaining 11 to 22 carbon atoms linked to the phenol nucleus by amethylene group.

11. A phenol sulphonate having a single openchain hydrocarbon radicalcontaining 13 to 18 carbon atoms linked to the phenol nucleus by amethylene group.

12. The method of making a sulphonated nuclear alkyl derivative ofphenol useful as a detergent, wetting agent, emulsifying agent, and thelike, which comprises sulphonating a nuclear monoalkyl derivative ofphenol and its monomethyl derivatives, having at least 11 carbon atomsin an open-chain hydrocarbon radical linked to the phenol nucleus by amethylene group.

13. The method of making a sulphonated nuclear monoalkyl derivative ofphenol useful as a detergent, wetting agent, emulsifying agent, and thelike, which comprises sulphonating a nuclear alkyl derivative of phenoland its monomethyl derivatives having 11 to 22 carbon atoms in a singleopen chain hydrocarbon radical linked to the phenol nucleus by amethylene group and resulting from the reduction of the correspondingalkyl keto phenol followed by fractional distillation of the reductionproduct and collection of a fraction of purified alkyl phenol.

14. Compounds having in the form of the free sulphonic acids thefollowing general formula I on RCHr' BOaH wherein.R represents astraight chain alkyl group containing from 11 to 17 carbon atoms.

15. Compounds having in the form of the free sulphonic acids the generalformula RCHs- OaH in which R. represents an alkyl hydrocarbon radicalcontaining 11 to 22 carbon carbon atoms, the alkyl radicals representedby B being derived from a mixture of fatty acids obtained from a naturalproduct.

19. Primary dodecyl phenol monosulphonate.

jLAwRnNcE H. mm.

. v CERTIFICATE OF CORRECTION. Patent No. 2,205,9 L8- June 25; I9LLO.-

LAWRENCE H. FLETT. g

It is hereby certified that error appears in. the printed specificationof the above numbered patent requiring correction as follows: Page )4,first column, linef55', claim8, for the word "so" read --to--; andsecond column, line 111., claim 15, for "monoalky1"' read --alkyl--;line 1?, same claim, for "alkyl' read -monoalky lL- line 57, claim 18,for "carbon carbon atoms" read -carbon atomsand that the said LettersPatent shouldbe read with this correction therein that thesame mayconform to the record of the case in the Patent Office.

Signed and sealed .this 5rd day of September, A. D. 191p.

Henry Van Arsdale, (Seal) Acting Commissioner of Patents.

